CN1237986A - Use of polyether polyurethane for protective clothing - Google Patents

Use of polyether polyurethane for protective clothing Download PDF

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Publication number
CN1237986A
CN1237986A CN97199807A CN97199807A CN1237986A CN 1237986 A CN1237986 A CN 1237986A CN 97199807 A CN97199807 A CN 97199807A CN 97199807 A CN97199807 A CN 97199807A CN 1237986 A CN1237986 A CN 1237986A
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CN
China
Prior art keywords
polyether
protective clothing
composition
polyurethane
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN97199807A
Other languages
Chinese (zh)
Other versions
CN1175019C (en
Inventor
K·布雷赫特
H·-D·阿恩茨
B·约翰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
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Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of CN1237986A publication Critical patent/CN1237986A/en
Application granted granted Critical
Publication of CN1175019C publication Critical patent/CN1175019C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2410/00—Soles

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the use of cellular to solid moulded plastics produced from polyether polyurethanes for producing soles for protective clothing, in particular protective boots.

Description

Polyether-polyurethane is used for the purposes of protective clothing
The present invention relates to be used to make protective clothing from porous to closely knit moulded plastics, the purposes at the bottom of the footwear especially by polyether-polyurethane production.
Mold pressing polyurethane-base plastics are known in decades prior arts.This class moulded plastics can be produced with the density and hardness scope of wide region, is used for various uses, for example as protective clothing.
The main application of urethane in protective clothing is as footwear.According to the structure of relevant footwear and the current standards of performance (EN344 and following), the selection of material up to this point is limited in the use polyester-polyurethane always.The major cause of getting rid of polyether-polyurethane is that the oil-proofness and the petrol-resistance (EN344,4,8,9 points, fuel resistance) of this material is good inadequately.
But, polyester-polyurethane or produce each required composition of polyester-polyurethane by the reaction injection molding(RIM) method and demonstrate following shortcoming:
Preparing to add man-hour, the high viscosity of each composition causes disadvantageous moulding
The required high temperature of each composition processing can contract its working life
When especially using at agriculture field or in the warm area, the deficiency of hydrolytic resistance and anti-microbial attack also can cause the storage period of finished product footwear restricted
The low temperature flexibility of standard polyester urethane is poor
As the processing of polyester-polyurethane, adopting reaction casting or reaction injection molding(RIM) method to produce polyether-polyurethane also is the part of prior art.As requested, at the bottom of individual layer and the double-deck mold pressing and directly, use the polyester-polyurethane of different densities and hardness to produce playshoes, playshoes and sports shoes in the system end method.
Because polyether based polyurethanes is newly developed, is surprisingly found out that now the occasion that so a kind of urethane is used for footwear demonstrates enough fuel resistances.
The purposes that is used to produce protective clothing to closely knit mold pressing polyether-based plastics from porous that the invention provides that the foam mold pressing produces.
The protective clothing that meets 344 pages of standards of EN (fuel resistance in octane-iso＜12% volume) for example is footwear, boots, apron etc.
This fuel resistance is use-case polyester-polyurethane system starting material as described below with 〉=800kg/m 3The substrate loose density reach.
From porous to closely knit polyether-polyurethane basic mode compression molding material is to carry out the foam mold pressing by the reaction mixture that will for example prepare from following ingredients to produce.
A) higher molecular weight polyether glycol composition,
B) polyisocyanates composition,
C) chain propagation agent,
D) optional foaming agent,
E) activator and optional,
F) further auxiliary substance and additive.
Wherein these raw materials are reacted in 70～130 scopes keeping isocyanate index.
Polyether glycol composition hydroxy functionality a) of higher molecular weight is 2.00, and perhaps comprising basically from the average hydroxy functionality of following ingredients preparation is 2.02～2.95 mixture:
Aa) at least a hydroxyl value is 10～115 polyether glycol, this glycol is produced by following method: make a kind of two sense initiator propoxylations, make the propoxylation products ethoxylation then, make the weight ratio of propylene oxide and ethylene oxide maintain 60: 40 simultaneously～85: 15 and
Ab) at least a hydroxyl value is 12～56 polyether triol, the filler that randomly contains styrene-based/acrylonitrile copolymer, polyureas or poly-hydrazono-methane amide, for composition gross weight a), its amount is at most 20% (weight), the preparation method of this polyether triol is: make trifunctional initiator propoxylation, make the weight ratio of propylene oxide and ethylene oxide maintain 60: 40 then～85: 15.
Polyisocyanates composition b) is a kind of isocyanate groups that contains, and NCO content is half heteropolymer of 10～25% (weight), it is by (ⅰ) 4,4 '-diisocyanate based ditane is 10～11 5 with (ⅱ) a kind of hydroxyl value, (on average) hydroxy functionality is 2.0～2.5, the polyether components and/or the hydroxyl value that are made of the mixture of at least a polyether glycol or at least a such glycol and at least a polyether triol are 28～115, average functionality is 2.0～2.5 polyester composition prepared in reaction, wherein said polyether glycol is to carry out propoxylation by two sense initiators, randomly using for the weight of this polyether glycol at the most the oxyethane of 40% weight that propoxylation products is carried out ethoxylation then prepares, and described polyether triol is to carry out propoxylation by the trifunctional initiator, randomly using for the weight of this polyether triol at the most the oxyethane of 40% weight that propoxylation products is carried out ethoxylation then prepares, wherein composition (ⅰ) randomly added before reaction, or to join the polypropylene glycol molecular weight be in 134～700 the reaction product and/or by making the weight with respect to composition (ⅰ), its amount be at most the liquefaction 4,4 of 10% weight '-the part isocyanate groups carbodiimideization of diisocyanate based ditane and in the reaction product that obtains.
1 and/or 1,4-butyleneglycol and/or Diethylene Glycol and/or trolamine and/or diethyl toluene diamine are as composition c),
And water and/or pneumatogen, for example R134a (hydro fluoroalkanes mixture) is then randomly as ingredient d).
Admissible activator e) is own compound known in the polyurethane chemistry, for example three hexylidene diamines, N, N-dimethyl benzylamine or organo-tin compound, for example dibutyl tin laurate or stannous octoate (II).
The auxiliary substance of the further use that can mention for example and additive f) be tensio-active agent, suds-stabilizing agent, abscess conditioning agent, interior with stripper, dyestuff, pigment, hydrolysis stabilizer, system is mould and bacteriostatic activity agent, photostabilizer, antioxidant and static inhibitor (quaternary ammonium compound).
Urethane is produced according to known prior art.Usually, this expression with composition a) and c) to f) merge to form " polyhydroxy reactant ", make it then in airtight mould, for example in airtight metal or mould of plastics with polyisocyanates composition b) react with one step, wherein use two traditional component mixed cells.Join the amount of the reaction mixture in the mould and as whipping agent and optional water and/or the pneumatogen that uses, for example R134 Amount calculate by this way in the method, promptly the loose density of resulting extruded foam is 〉=800kg/m 3The most important applications field is shoemaking, is to be used to produce that footwear uses from porous to closely knit sole according to the present invention.The loose density of the sole of this footwear better 〉=800kg/m 3, and in a specific embodiments, with loose density 〉=400kg/m 3The sole middle layer link to each other.
Example
The prescription that following example explanation is used at the bottom of the protective shoe is formed.In all examples, all keeping isocyanate index is 100.As sample, be used to measure mechanical property and petrol-resistance (EN344, point 4,8,9) with the test piece that is of a size of 20 * 20 * 1cm.
Starting material
Polyol a)
a 1Polyether glycol, OH value 28, PO/EO weight ratio 70: 30
a 2Polyether glycol, OH value 28, PO/EO weight ratio 77: 23
Polyisocyanates b)
4,4 '-reaction product of diisocyanate based ditane (MDI) and tripropylene glycol, NCO content 23%.
Example:
The prescription of example 1-3 is shown in following table 1, and mechanical property and petrol-resistance then are shown in table 2.
Table 1 (all data are weight part)
Example 1 Example 2 Example 3
Composition a 1 ????90.00 ????79.27 ????71.55
Composition a 2 ?????-- ????10.00 ????20.00
1, the 4-butyleneglycol ????6.00 ????7.50 ?????--
1 ?????-- ????0.50 ?????--
Diethyl methylene phenyl diamines ?????-- ?????-- ????6.00
Triethylenediamine ????1.80 ????0.60 ????0.20
Dibutyl tin laurate ????0.05 ????0.03 ????0.05
Trolamine ????0.15 ?????-- ????0.20
Water ?????-- ????0.10 ????--
Sulfuric acid tetra-allkylammonium (Catafor CA 100) ????2.00 ????2.00 ????2.00
Polyisocyanates b) ????33 ????44 ????26
Table 2: mechanical property
Example 1 Example 2 Example 3
????DIN?54320 (kg/m 3) ????1100 ????900 ????1080
Hardness DIN 53505 (Shore A) ????60 ????60 ????70
Tensile strength DIN 53504 (MPa) ????16 ????8 ????12
Extension at break DIN53504 (％) ????800 ????600 ????610
Anti tear spreads intensity DIN53516 (kN/m) ????18 ????10 ????20
Fuel resistance EN 344 (% volume change) ????9.5 ????10.5 ????11.5

Claims (4)

1．从多孔到密实的模压聚醚基塑料用于模压发泡制造防护服的用途。1. The use of molded polyether-based plastics from porous to dense for molded foam to make protective clothing. 2．按照权利要求1的用途，用于制造防护鞋鞋底。2. Use according to claim 1 for the manufacture of protective shoe soles. 3．按照权利要求2的用途，其特征在于该鞋底的松密度为≥800kg/m3。3. Use according to claim 2, characterized in that the bulk density of the sole is ≥ 800 kg/m 3 . 4．按照权利要求2的用途，其特征在于该鞋底与松密度≥400kg/m3的鞋底中间层相连。4. Use according to claim 2, characterized in that the sole is connected to a midsole with a bulk density ≥ 400 kg/m 3 .
CNB971998078A 1996-11-22 1997-11-10 Use of polyether polyurethane for protective clothing Expired - Fee Related CN1175019C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19648509A DE19648509A1 (en) 1996-11-22 1996-11-22 Use of polyether PUR for safety clothing
DE19648509.6 1996-11-22

Publications (2)

Publication Number Publication Date
CN1237986A true CN1237986A (en) 1999-12-08
CN1175019C CN1175019C (en) 2004-11-10

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CNB971998078A Expired - Fee Related CN1175019C (en) 1996-11-22 1997-11-10 Use of polyether polyurethane for protective clothing

Country Status (13)

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US (1) US6521676B2 (en)
EP (1) EP0939780B1 (en)
JP (1) JP2001506676A (en)
KR (1) KR100522989B1 (en)
CN (1) CN1175019C (en)
AU (1) AU5551398A (en)
DE (2) DE19648509A1 (en)
ES (1) ES2172824T3 (en)
IL (1) IL129858A (en)
PT (1) PT939780E (en)
TR (1) TR199901098T2 (en)
TW (1) TW460497B (en)
WO (1) WO1998023659A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1315901C (en) * 2002-10-14 2007-05-16 拜尔材料科学股份公司 Microcellular polyurethane elastomers, method for the production thereof and use thereof
CN104757722A (en) * 2015-04-01 2015-07-08 大连华工创新科技股份有限公司 E-TPU foaming protecting clothing
CN104945594A (en) * 2015-05-29 2015-09-30 德州市鑫华润聚氨酯鞋材股份有限公司 Polyurethane with characteristics of hydrolysis resistance and low temperature resistance, and preparation method thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19927188A1 (en) * 1999-06-15 2000-12-21 Bayer Ag Polyurea polyurethanes with improved physical properties
US20040154718A1 (en) * 2003-02-06 2004-08-12 Doesburg Van I. Polyurethane filled tire and method of making same
DE102004009939A1 (en) * 2004-02-26 2005-09-15 Basf Ag Swelling resistant polyurethane integral foams
ITMI20101084A1 (en) * 2010-06-16 2011-12-16 Dow Global Technologies Inc POLYURETHANE SOLES OF SHOES PREPARE USING PROPYLENE OXIDE-BASED POLYOLS

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1315901C (en) * 2002-10-14 2007-05-16 拜尔材料科学股份公司 Microcellular polyurethane elastomers, method for the production thereof and use thereof
CN104757722A (en) * 2015-04-01 2015-07-08 大连华工创新科技股份有限公司 E-TPU foaming protecting clothing
CN104945594A (en) * 2015-05-29 2015-09-30 德州市鑫华润聚氨酯鞋材股份有限公司 Polyurethane with characteristics of hydrolysis resistance and low temperature resistance, and preparation method thereof

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JP2001506676A (en) 2001-05-22
AU5551398A (en) 1998-06-22
US20020013377A1 (en) 2002-01-31
DE19648509A1 (en) 1998-05-28
CN1175019C (en) 2004-11-10
EP0939780B1 (en) 2002-02-13
TR199901098T2 (en) 1999-07-21
KR20000057180A (en) 2000-09-15
WO1998023659A1 (en) 1998-06-04
ES2172824T3 (en) 2002-10-01
EP0939780A1 (en) 1999-09-08
DE59706407D1 (en) 2002-03-21
KR100522989B1 (en) 2005-10-21
PT939780E (en) 2002-07-31
TW460497B (en) 2001-10-21
IL129858A0 (en) 2000-02-29
US6521676B2 (en) 2003-02-18
IL129858A (en) 2003-05-29

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